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Enthalpy-Controlled Insertion of a “Nonspectator” Tricoordinate Phosphorus Ligand into Group 10 Transition Metal–Carbon Bonds
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nihms-1654395.pdf
Description
Accepted version
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1.43 MB
Format
Adobe PDF
Checksum (MD5)
8c42a54b80030d0dfc32df694847ac8d
Author(s)
Hwang, Seung Jun
Tanushi, Akira
Radosevich, Alexander T
Date Issued
2020
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Hwang, Seung Jun, Tanushi, Akira and Radosevich, Alexander T. 2020. "Enthalpy-Controlled Insertion of a “Nonspectator” Tricoordinate Phosphorus Ligand into Group 10 Transition Metal–Carbon Bonds." Journal of the American Chemical Society, 142 (51).
Version
Author's final manuscript
Abstract
© Insertion of a tricoordinate phosphorus ligand into late metal-carbon bonds is reported. Metalation of a P^P-chelating ligand (L1), composed of a nontrigonal phosphorous (i.e., P(III)) triamide moiety, P(N(o-N(Ar)C6H4)2, tethered by a phenylene linker to a -PiPr2 anchor, with group 10 complexes L2M(Me)Cl (M = Ni, Pd) results in insertion of the nontrigonal phosphorus site into the metal-methyl bond. The stable methylmetallophosphorane compounds thus formed are characterized spectroscopically and crystallographically. Metalation of L1 with (cod)PtII(Me)(Cl) does not lead to a metallophosphorane but rather to the standard bisphosphine chelate (κ2-L1)Pt(Me)(Cl). These divergent reactivities within group 10 are rationalized by reference to periodic variation in M-C bond enthalpies.
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DOI of Published Version
10.1021/JACS.0C11161
